Triazolyl phosphorus compounds

ABSTRACT

Triazolylphosphorus compounds of the formula   WHEREIN R1 represents hydrogen, alkyl, cycloalkyl, phenyl, benzyl or phenethyl, R2 represents alkylthio, alkylsulphinyl, alkylsulphonyl, phenthio, phenylsulphinyl, phenylsulphonyl, benzylthio, benzylsulphinyl or benzylsulphonyl, R3 represents alkyl, alkoxy, alkylthio or phenyl, R4 represents alkyl, and X represents oxygen or sulphur, PROCESSES FOR THEIR PRODUCTION AND THEIR USE FOR PEST CONTROL.

United States Patent [191 Bohner et al.

[ 1 Feb. 18,1975

[ TRIAZOLYL PHOSPHORUS COMPOUNDS [75] Inventors: Beat Bohner, Binningen;Dag Dawes,

Pratteln; Willy Meyer, Basel, all of [211 Appl. No.: 310,728

[30] Foreign Application Priority Data Dec. 10, 1971 Switzerlandl8064/7l Sept. 29. 1972 Switzerland l4254/72 [52] U.S. Cl. 260/308 R,424/200 [5 l] Int. Cl C07d 55/06 [58] Field Of Search 260/308 R [56]References Cited OTHER PUBLICATIONS Chemical Abstracts, Vol. 71, 1969,Item l0l86l(e) page 355, Abstracting South African Patent 68/()3,47l 3!Oct., 1968.

Primary Examiner-Henry R. Jiles Assistant Examiner-Robert T. BondAttorney, Agent, or Firm-Harry Falber; Frederick H. Rabin [57] ABSTRACTTriazolylphosphorus compounds of the formula l R 2 N wherein Rrepresents hydrogen, alkyl, cycloalkyl, phenyl,

benzyl or phenethyl,

R represents alkylthio, alkylsulphinyl, alkylsulphonyl, phenthio,phenylsulphinyl, phenylsulphonyl, benzylthio, benzylsulphinyl orbenzylsulphonyl,

R represents alkyl, alkoxy, alkylthio or phenyl,

R represents alkyl, and

X represents oxygen or sulphur,

processes for their production and their use for pest control.

8 Claims, No Drawings TRIAZOLYL PHOSPHORUS COMPOUNDS The presentapplication relates to triazolylphosphorus compounds and to processesfor their production, as well as to their use for pest control.

The triazolylphosphorus compounds correspond to the formula l y l. R, R(I) wherein R represents hydrogen, alkyl, cycloalkyl, phenyl,

benzyl or phenethyl,

R represents alkylthio, alkylsulphinyl, alkylsulphonyl, phenthio,phenylsulphinyl, phenylsulphonyl, benzylthio, benzylsulphinyl orbenzylsulphonyl,

R represents alkyl, alkoxy, alkylthio or phenyl,

R represents alkyl, and

X represents oxygen or sulphur.

By the terms alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonylradical is meant in each case a straight-chain or branched radicalhaving 1 to 12, preferably l to 6, carbon atoms, the said radical beingunsubstituted or substituted by halogen, such as fluorine, chlorine,bromine and/or iodine, particularly fluorine or chlorine. Examples ofsuch radicals are inter alia': methyl, methoxy, methylthio,methylsulphinyl, methylsulphonyl, ethyl, ethoxy, ethylthio,ethylsulphinyl, ethylsulphonyl, 2,2,2-trichloroethyloxy, 2,2,2-trifluoroethyloxy, propyl, propoxy, nand sec.- propylthio,propylsulphinyl, propylsulphonyl, n-butyl, n-butoxy, n'butylthio, i-,sec.-, tert.-butyl, n-pentyl, npentoxy, n-pentylthio.

The cycloalkyl radicals denoted by R contain 3 to 8 ring carbon atoms.Preferred cycloalkyl radicals are cyclopropyl, cyclopentyl orcyclohexyl.

The phenyl, benzyl and phenethyl groups denoted by R, can beunsubstituted on the rings, or substituted, for example, by methoxy,halogen atoms such as fluorine, chlorine, bromine and/or iodine,preferably chlorine, and/or C,C -alkyl.

Of special importance because of their effectiveness are compounds offormula I wherein R represents hydrogen, C,C -alkyl, cyclopentyl, cy-

clohexyl, benzyl, phenethyl, phenyl, 3- chlorophenyl, 3-methylphenyl,3-methyl-4- ehlorophenyl, 2-methyl-4-chlorophenyl, 4- isopropylphenyl,3-chloro-4-methoxyphenyl or 3,4-dichlorophenyl,

R represents C C -alkylthio, C -C -alkylsulphinyl, C,-Cr,-alkylsulphonyl, phenthio, phenylsulphinyl. phcnylsulphonyl orbenzylthio, benzylsulphinyl, benzylsulphonyl,

R represents methyl, ethyl, methoxy, ethoxy, C -C alkylthio or phenyl,

R represents methyl, ethyl or propyl, and

X represents oxygen or sulphur.

The compounds can be produced by methods known per se, e.g. by thereaction of a. a hydroxy-triazole of the formula u R Hal- 0 R b. ahydroxy-triazole of the formula (III) 4 U R N OMe with a compound of theformula wherein R to R, and X have the meanings given for formula I, Halstands for a halogen atom, particularly for chlorine or bromine, and Mestands for a monovalent metal, especially an alkali metal.

Suitable acid-binding agents are, for example, the following bases:tertiary amines such as triethylamine, dimethylaniline, pyridine,inorganic bases such as hydroxides and carbonates of alkali andalkaline-earth metals, preferably sodium and potassium carbonate.

The reactions are preferably carried out in solvents or diluents whichare inert to the reactants. The following, for example, are suitable forthis purpose: aromatic, hydrocarbons such as benzene, toluene, ligroins,halogenated hydrocarbons, chlorobenzene, polychlorobenzenes;bromobenzene, chlorinated alkanes having 1 to 3 carbon atoms; etherssuch as dioxane, tetrahydrofuran; esters such as ethyl acetate; ketonessuch as acetone, methyl ethyl ketone, diethyl ketone. nitriles, e.g.acetonitrile, etc..

The starting materials of formulae ll and IV are in some cases knowncompounds that can be produced, e.g. by a method analogous to thatdescribed in Chem. Ber. 56 B, 2276-83 (1923).

These compounds can be produced also by reaction of a5-halogeno-3-hydroxy-l ,2,4-triazole derivative with metal salts ofmcrcaptans or thiophenols.

Finally, a number of these compounds can moreover be obtained by thereaction of 5-mcrcapto-3hydroxyl,2,4-triazole with an alkylating agent,such as, eg alkylhalide or a dialkylsulphate, in the presence of a base.

The compounds of formula I have a broad biocidal action, and can be usedfor the control of diverse plant and animal pests. The said compoundsare suitable, in particular, for the control of insects of the families:Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae,Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae,Diaspididae, Pseudococ- (III) cidae, Chrysomelidae, Coccinellidae,Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae,Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae,Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae,as well as acarids of the families: lxodidae, Argasidae, Tetranychidae,Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadenedand adapted to suit the particular circumstances by the addition ofother insecticides and/or acaricides.

Suitable additives include, for example, the following activesubstances:

Organic phosphorus compounds Bis- 0,0'diethylphosphoric acid anhydride(TEPP) Dimethyl-( 2,2,2-trichloro- 1 -hydroxyethyl phosphonate(TRICHLORFON) l,2dibromo-2,2-dichloroethyldimethylphosphate (NALED)2,Z-dichlorovinyldimethylphosphate (DICHLORVOS) Z-methoxycarbamyll-methylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-(methylcarbamoyl vinylphosphate cis (MONOCROTOPHOS)3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS)2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-diethyl-(or S)-2-(ethylthio-ethylthiophosphate(DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate OMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-2-ethylthio)ethyldithiophosphate SULFOTON)0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL)0,0-dimethyl-S-( l,2-dicarbethoxyethyldithiophosphate (MALATHION)0,0,0,0-tetraethyl-S,S-methylene-bis-dithiophosphate (ETHION)O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate MOTHION)0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE)(THI- (FOR- 0,0-dimethyl-O-p-nitrophenylthiophosphate (PA-RATHlON-METHYL) 0,0-diethyl-0-p-nitrophenylthiophosphate (PARA- THION)O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)0,0-dimethyl-0-(4-nitro-m-tolyl)thiophosphate (FENl- TROTHION)0.0-dimethyl-O-2,4-5-trichlorophenylthiophosphate (RONNEL)0-ethyl-0.2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE)(LO-dimethyl-O-Z,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)()-dimcthyl-0-(2,5-dichloro-4-jodphenyl)- thiophosphate (JODOFENPHOS)4-tert. butyl-2-chlorophenyl-N-methyl-0- methylamidophosphate(CRUFOMATE) 4 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl)-thiophosphate (FENTHION) lsopropylamino-O-ethyl-O-(4-methylmercapto-3-methylphenyU-phosphatc0,0-diethyl-O-p-(methylsulphinyl)phenylthiophosphate (FENSULFOTHION)O-p-(dimethylsulphamido)phcnyl-0,0-dimcthylthiophosphate (FAMPHUR)0,0,0',O-tetramethyl-(),0'-thiodi-p-phenylcnethiophosphateO-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl0-(a-methylbenzyl-3-hydroxycrotonyl phosphate2-chloro-l-(2,4-dichlorophenyl)vinyldiethylphosphate (CHLORFENVINPHOS)l-chloro-l-(2,4,5-trichlorophenyl)vinyldimethylphosphate0-[2-chloro-l-(2,5-dichlorophenyl)]vinyl-0,0-diethylthiophosphatePhenylglyoxylonitriloxim-0,0-diethylthiophosphate (PHOXIM)0,0-diethyl-O-( 3-chloro-4-methyl-2-oxo-2-H- l benzopyran-7-yl)-thiophosphate (COUMAPHOS)2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION)5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl10,0-

diethyldithiophosphate (PHOSALONE) 2-(diethoxyphosphinylimino)-l,3-dithiolanc 0,0-dimethyl-S-[ 2-methoxy-l ,3,4-thiadiazolonyl-(4)-methylldithiophosphate0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN)0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)thiophosphatc0,0-diethyl-O-Z-pyrazinylthiophosphate (THIONA- ZlN)0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (DIAZINON)0,0-diethyl-0-(Z-chinoxalyl)thiophosphate 0,0-dimethyl-S-(4-oxo-l,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate (AZINPHOSMETHYL)0,0-diethyl-S-(4-oxo-l ,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate(AZINPHOSETHYL)S-[(4,6-diamino-s-triazin-2-yl)methyl]-0,0-dimethyldithiophosphate(MENAZON) 0,0-dimethyl-O-( 3-chloro4-nitrophenyl )thiophosphate(CHLORTHION) 0,0-dimethyl-0( or S)-2-(ethylthioethyl)thiophosphate(DEMETON-S-METHYL)2(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxypyron-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride0,0-diethy|-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON)0,0-diethyl-O-(4-methyl-cumarinyl-7-)-thiophosphate (POTASAN)5-amino-bis(dimethylamido)phosphinyl-3-phenyl- 1,2,4-triazole(TRIAMIPHOS) N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiava|- eramide(VAMlDOTHlON) 0,0-diethyl-0-l 2-diemthylamino-4-methyIpyrimidyH6)]-thiophosphate (DlOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyU-thiophosphate (OMETHOATE) 0-ethyI-O-(8-quinolinyl)phenylthiophosphonate(OX INOTHIOPHOS) O-methyl-S-methyl-amidothiophosphate (MONITOR) 93-isopropylphenyl-N-methyl-N-chloroacetylcarbamate3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamate2,2-dimethyl-4-chloro-2,3-dihydro-7- benzofuranyl)-N-methylcarbamate 0-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl )-N- methylcarbamate0-naphthyl-NmethyLN-acetyl-carbamate0-5,6,7,S-tetrahydronaphthyl-N-methyl-carbamate3-isopropy1-4-methylthio-phenyl-N-methylcarbamate3,S-dimethyl-4-methoxy-phenyl-N-methylcarbamate3-methoxymethoxy-phenyl-N-methylcarbamate3-allyloxyphenyl-N-methylcarbamate2-propargyloxymethoxy-phenyl-N-methyl-carbamateZ-allyloxyphenyhN-methyl-carbamate4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamateZ-y-methylthiopropylphenyl-N'methyl-carbamate 3-(a-methoxymethyl-Z-propenyl )-phenyl-N-methylcarbamate2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate 4-(methyl-propargylamino )-3 ,S-xylyl-N-methylcarbamate 4-(methyl-y-chloroallylamino )-3 ,5-xylyl-N-methylcarbamate 4-(methyHB-chloroallylamino)-3,5-xylyl-N-methyl carbamate1(B-ethoxycarbonalethyl )-3-methyl-5-pyrazolyl-N,N-

dimethylcarbamate3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)phenyl-N-methylcarbamatel,3-bis( carbamoylthio)-2-(N,N-dimethylamino)- propanehydrochloride5,5-dimethylhydroresorcinoldimethylcarbamate2-[ethyl-propargylamino]-phenyl-N-methylcarbamate 2-[methyl-propargylamino]-phenyl-N- methylcarbamate 2'[dipr0pargylamino1-phe nyl-N-methylcarbamate4[dipropargylamino]-3-tolyl-N-methylcarbamate4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate2[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]phenyl-N-methylcarbamate CHLORINATED HYDROCARBONS'y-hexachlorocyclohexane [GAMMEXANE; LINDAN;

y HCH] l,2,4,5,6,7,8,8-octachloro-3a,4,7,7a'tetrahydro-4,7-

methylenindane [CHLORDAN] l,4,5,6,7,8,8-heptachloro,3a,4,7,7a-tetrahydro-4,7-

methylenindane [HEPTACHLOR] 1,2,3,4,l O, l O-hexachloro-l,4,4a,5,8,8a-hexahydroendol ,4-exo-5,S-dimethanonaphthalene [ALDRIN]l,2,3,4,l0,lO-hexachloro-6,7-epoxy-l ,4,4a,5,6,7,8,8aoxtahydro-exo-l,4-endo-5 ,S-dimethanonaphthalene [DIFLORIN] l,2,3,4, l 0, l0-hexachloro-5,7 epoxy-l ,4,4a,5,6,7,8,8a-

octyhydro-endo-endo-S,8-dimethanonaphthalene [ENDRIN] in addition topossessing the above mentioned properties, the compounds of formula Iare moreover effective against members ofthe division Thallophyta. Someof these compounds thus have a bactericidal action. They are, however,particularly effective against fungi, especially against thephytopathogenic fungi belonging to the following classes: Oomycetes,Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compoundsof formula I also have a fungitoxic action in the case of fungi whichattack the plants from the soil. Furthermore, the new active substancesare suitable for the treatment of seed, fruit, tubers, etc., forprotection against fungus infections. The compounds of formula I aresuitable too for the control of phytopathological nematodes.

The compounds of formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives maybe solid or liquid, and correspond to the substances common informulation practice, such as, eg natural and regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisersv For application, the compounds of formula Ican be processed into the form of dusts, emulsion concentrates,granulates, dispersions, sprays, or solutions, the formulation of thesepreparations being effected in a manner commonly known in practice. Alsoto be men tioned are cattle dips and spray races, in which aqueouspreparations are used.

The agents according to the invention are produced in a manner known perse by the intimate mixing and- /or grinding of active substances offormula I with the suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the followingpreparation forms:

solid preparations:

dusts, scattering agents, granulates,

coated granulates, impregnated granulates and homogeneous granulates;liquid preparations:

a. water dispersible active substance concentrates:

wettable powders, pastes, emulsions;

1). solutions.

The solid preparations (dusts, scattering agents) are produced by themixing of the active substances with solid carriers. Suitable carriersare, e.g. kaolin, talcum, bole, loess, chalk, limestone, groundlimestone, attapulgite, dolomite, diatomaceous earth, precipitatedsilicic acid, alkaline-earth silicates, sodium and potassium aluminiumsilicates (feldspar and mica), calcium and magnesium sulphates,magnesium oxide, ground synthetic materials, fertilisers such asammonium sulphate, ammonium phosphate, ammonium nitrate, urea, groundvegetable products such as bran, bark dust, sawdust, ground nutshells,cellulose powder, residues of plant extractions, active charcoal, etc.,alone or in admixture with each other.

Granulates can be very easily prepared by a process in which an activesubstance of formula I is dissolved in an organic solvent, the thusobtained solution applied to a granulated mineral, e.g. attapulgite, SiOgranicalcium, bentonite, etc., and the organic solvent then evaporatedoff.

It is possible also to produce polymer granulates; in this case theactive substances of formula I are mixed with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde,or others); polymerisation is then carefully carried out in a mannerwhich leaves the active substances unaffected, and granulation performedactually during the gel forming process. it is more favourable, however,

to impregnate finished porous polymer granules (urea/- formaldehyde,polyacrylonitrile, polyester and others), having a specific surface areaand a favourable predeterminable adsorption/desorption ratio, with theactive substances, e.g. in the form of their solutions (in a lowboilingsolvent), and to then remove the solvent. Polymer granulates of thiskind can be also sprayed in the form of microgranulates, having bulkweights of preferably 300 g/litre to 600 g/litre, with the aid of sprayapparatus. Spraying can be carried out over extensive areas of usefulplant crops by the use of aeoplanes.

Granulates can also be obtained by the compacting of the carriermaterial with the active substances and additives, and a subsequentreducing operation.

Moreover, it is possible to add to these mixtures additives stabilisingthe active substance and/or nonionic, anion-active and cation-activesubstances which improve, e.g. the adhesiveness of the active substanceson plants and parts of plants (adhesives and agglutinants), and/orensure a better wettability (wetting agents) as well as dispersibility(dispersing agents).

The following substances are, for example, suitable: olein/lime mixture,cellulose derivatives (methyl cellulose, carboxymethyl cellulose),hydroxyethylene glycol ethers of monoalkyl and dialkyl phenols having toethylene oxide radicals per molecule and 8 to 9 carbon atoms in thealkyl radical, ligninsulphonic acid, the alkali metal and alkaline-earthmetal salts thereof, polyethylene glycol ethers (carbowaxes), fattyalcohol polyglycol ethers having 5 to ethylene oxide radicals permolecule and 8 to 18 carbon atoms in the fatty alcohol moiety,condensation products of ethylene oxide, propylene oxide,polyvinylpyrrolidones, polyvinyl alcohols, condensation products of ureaand formaldehyde, as well as latex products.

Water-dispersible concentrates of active substances, i.e. wettablepowders, pastes and emulsion concentrates, are agents which can bediluted with water to obtain any desired concentration. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substances, and anti-foam agents and,optionally, solvents.

The wettable powders and pastes are obtained by the mixing and grindingof the active substances with dispersing agents and pulverulentcarriers, in suitable devices, until homogeneity is obtained. Suitablecarriers are, e.g. those previously mentioned in the case of solidpreparations. It is advantageous in some cases to use mixtures ofdifferent carriers. As dispersing agents it is possible to use, e.g.:condensation products of sulphonated naphthalene and sulphonatednaphthalene derivatives with formaldehyde, condensation products ofnapthalene or of naphthalenesulphonic acids with phenol andformaldehyde, as well as alkali, ammonium and alkaline-earth metal saltsof ligninsulphonic acid, also alkylarylsulphonates, alkali metal saltsand alkalineearth metal salts of dibutyl naphthalenesulphonic acid,fatty alcohol sulphates such as salts of sulphated hexadecanols,heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycolethers, the sodium salt of oleyl methyl tauride, ditertiary ethyleneglycols, dialkyl dilauryl ammonium chloride, and fatty acid alkalimetaland alkaline-earth metal salts.

Suitable anti-foam agents are, e.g. silicones.

The active substances are so mixed, ground, sieved and strained with theabove mentioned additives that the solid constituent in the case ofwettable powders has a particle size not exceeding 0.02 to 0.04 mm, andin the case of pastes not exceeding 0.03 mm. For the preparation ofemulsion concentrates and pastes, dispersing agents are used such asthose mentioned in the preceding paragraphs, organic solvents and water.Suitable solvents are, e.g. alcohols, benzene. xylene, toluene,dimethylsulphoxide, and mineral oil fractions boiling in the range ofl20 to 350C. The solvents must be practically odourless, nonphytotoxic,and inert to the active substances.

Furthermore, the agents according to the invention can be used in theform of solutions. For this purpose, the active substance, or severalactive substances, of the general formula l is dissolved in suitableorganic solvents, solvent mixtures, or water. As organic solvents it ispossible to use aliphatic and aromatic hydrocarbons, their chlorinatedderivatives, alkylnaphthalenes, mineral oils on their own or inadmixture with each other.

The content of active substance in the above described agents is between0.1 and percent; it is to be mentioned in this connection that in thecase of appli cation of the agents from an aeroplane, or bymeans of someother suitable application devices, concentrations of up to 99.5 percentcan be used, or even the pure active substance.

The active substances of formula I can be prepared, e.g. as follows:

DUSTS The following substances are used for the preparation of a) a 5percent dust, and b) a 2 percent dust:

a) 5 parts of active substance 95 parts of talcum.

2 parts of active substance 1 part of highly dispersed silicic acid 97parts of talcum.

The active substances are mixed and ground with the carriers.

The following substances are used to produce a 5 7c granulate:

5 parts of active substance, 025 parts of epichlorhydrin. 0.25 parts ofcetyl polyglycol ether, 350 parts of polyethylene glycol, 91 parts ofkaolin (particle size 0.3 0.8 mm).

WETTABLE POWDER The following constituents are used for the preparationofa) a 40%, b) and c) a 25%, and d) a 10% wettable powder:

40 parts of active substance,

5 parts of sodium lignin sulphonate, 1 part of sodiumdibutyl-naphthalene sulphonatc.

54 parts of silicic acid. b) 25 parts of active substance,

4 parts of calcium lignin sulphonate l loin parts of Champagneehalk/hydroxyethyl cellulose mixture (l:l parts of sodium dibutylnaphthalene sulphonate,

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto given suspensions of any desired concentration.

EMULSIFlABLE CONCENTRATES The following substances are used to producea) a and b) a 25% emulsifiable concentrate:

parts of active substance.

3.4 parts of epoxidiscd vegetable oil.

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide.

432 parts of xylene.

b) 25 parts of active substance.

.5 parts of epoxidised vegetable oil,

parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5parts of dimethylformamide,

parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

SPRAY The following constituents are used to prepare a 5 percent spray:

5 parts of active substance. 1 part of epichlorhydrin. 94 parts ofligroin (hoiling limits IMP-190C).

EXAMPLE 1 Preparation of the Starting Materials a.1-lsopropyl-5-methylmercapto-3-hydroxy-1,2,4- triazole An amount of 19.6g of methylmercaptan is added at 5C, with stirring, to 200 ml of 5Naqueous sodium hydroxide solution. An addition is then made of 33 g ofl-isopropyl-5-chloro-3-hydroxy-l,2,4-triazole, and the mixture heatedfor 2 hours at 100C. After cooling to C, the solution is acidified bythe addition of potassium hydrogen sulphate, and extracted with ethylacetate. The ethyl acetate extract is dried over anhydrous magnesiumsulphate; it is then concentrated in a waterjet vacuum, and the residuecrystallised from a little methanol at -70C. The obtained product is 1-isopropyl-S-methylmercapto-3-hydroxyl ,2,4triazole with a melting pointof 90-92C.

The same compounds can be produced'also as follows:

A mixture of 15.9 g of l-isopropyl-5-mercapto-3- hydroxy-1,2,4-triazole,11.1 g of triethylamine and 15.6 g of methyliodide in 100 ml of methanolis maintained for 4 hours at 40C. The reaction mixture is concentratedto dryness in a water-jet vacuum; the residue is then taken up in 100 mlof water, and extracted twice with 200 ml of ethyl acetate each time.The organic phase is separated and concentrated by evaporation. Thereremains an amount of 16.5 g of crudelisopropyl-S-methylmercapto-l,2,4-triazolc. which has. afterrecrystallisation from ether, a melting point of 9092C.

b. l-Phenyl-5-methylmercapto-3-hydroxy-1,2,4-triazole An amount of 23.2g of l-phenyl-S-mercapto-l,2,4- triazole, MP. 220C, is placed into 50 mlof acetone, 50 ml of water and 10 ml of methyliodide. An addition isthen made in portions, within 15 minutes, of 21 g of sodium carbonate,and, after completion of the addition, stirring continued for 1 hour at30C. The acetone is evaporated off, and the solution acidified withdilute hydrochloric acid. The precipitated product is filtered off, andrecrystallised from 250 ml ofethanol to obtain1-phenyl-5-methylmercapto-3-hydroxy-l ,2,4-triazole in the form of whitecrystals having a melting point of 176177C.

c. l-Phenyl-5-methylsulphinyl-3-hydroxyl ,2,4-triazole An amount of 41.4 g of 1-phenyl-5-methylmercapto- 3-hydroxy-1,2,4.-triazole issuspended at 50C in 400 ml of ethyl acetate. An addition is then madedropwise.

within 15 minutes, of 60 ml ofa 60% solution of peroxyacetic acid inglacial acetic acid at 4550C. After completion of the addition, thesolution is stirred for 2 hours at 50C, and then cooled to 20C. Theprecipitated product is filtered off, washed with water, and dried invacuo. The resulting product is l-phenyl-S-methylsulphinyl-3-hydroxy-1,2,4-triazole in the form of white crystals,M.P. ll 82C.

d. 1-Phenyl-5-methylsulphonyl-3-hydroxy-l ,2,4-triazole An amount of16.5 g of 1-phenyl-5-methylmercapto- 3-hydroxy-1,2,4-triazole issuspended at 80C in 200 ml of ethyl acetate; an addition is then made,in portions, of 30 ml of a solution of 60 percent peroxyacetic acid inglacial acetic acid. The solution, which has become clear after acertain time, is refluxed for 4 hours. After cooling to 10C, theprecipitated crystals are filtered off, washed with water and dried tothus obtain 1- phenyl-S-methylsulphonyl-3-hydroxy-l,2,4-triazole in theform of white crystals having a melting point of 173-l75C.

e. 1-lsopropyl-5-phenyl-mercapto-3-hydroxy-1 ,2,4- triazole Amountsrespectively of 22 g of thiophenol, 16 g of sodium hydroxide and 32.3 gof l-isopropyl-5-chloro' 3-hydroxy-l ,2,4-triazole in 40 ml of water arerefluxed for 3 hours. The solution is thereupon cooled to 20C, andacidified with hydrochloric acid to obtain a pH- value of 5. Theprecipitated oil is taken up in ethyl acetate. The solvent is evaporatedoff and the residue recrystallised from acetonitrile. The thus obtainedproduct is l-isopropyl5-phenylmercapto-3-hydroxy-l,2,4- triazole in theform of colourless crystals having a melting point of l24l26C.

EXAMPLE 2 Preparation of the New Phosphorus Compounds a. 0,0-Diethyl--[l-isopropyI-S-methylmercapto-l ,2,4- triazolyl-( 3 )]-thiophosphateAmounts respectively of 9.0 g of l-isopropyl-5methylmercapto-3-hydroxy-l ,2,4-triazole, M.P. 9092C, and 7.0 g ofpotassium carbonate in 250 ml of methyl ethyl ketone are refluxed forone hour. An addition is subsequently made dropwise at 50C of 9.5 g of0,0-diethyl-thiophosphoric acid chloride, and the mixture refluxed fortwo hours. After the precipitated salts have been filtered off and thesolvent evaporated off in vacuo, there is obtained the compound of theformula HN N in the form of a pale yellow oil.

b. 0,0-diethyl-0-[ l-methyl-5-isoprorpylmercapto-l ,2,4- triazolyl-( 3)]-thiophosphate Amounts of 8.9 g of l-methyl-S-isopropylmercapto-3-hydroxy-l,2,4-triazole, M.P. 132l35C, and 7.0 g of potassium carbonateare refluxed in 300 ml of methyl ethyl ketone for two hours. Thesolution is cooled to room temperature and 9.8 g of0,0-diethyl-thiophosphoric acid chloride then added. Refluxing iscontinued for one hour. and the solution afterwards stirred at roomtemperature. The precipitated salts are filtered off through Hyflo, andthe solvent removed in vacuo from the clear filtrate; the residueremaining is the compound of the formula 0-Ethyl-O-[ l-phenyl-5-methylmercapto-1,2,4-triazolyl- (3 )l-ethyl-thiophosphonieacid ester Amounts of 20.7 g of l-phenyl-5-methylmercapto-3 hydroxy-l.2.4-triazole, M.P. l76l77C, and 13.8 g of potassium carbonate in 500 mlof methyl ethyl ketone are refluxed for 2 hours. The solution is cooledto room temperature and an addition then made dropwise of 17.3 g ofO-ethyl-ethylthiophosphonic acid chloride; the mixture is subsequentlyrefluxed for 2 hours. The precipitated salts are filtered off throughHyflo, and the filtrate concentrated in vacuo. The residue consists ofthe compound of the formula G I s a n H t CH Si l0 2 5 n 5 N C H D inthe form of pale yellow oil.

d. 0,0-Dimethyl-O-[ l-isopropyl-5-isopropylmercapto- 1,2,4-triazolyl-t 3I-thiophosphatc in the form of a pale yellow oil.

s I n n3 1,5082

e. 0,0-Diethyl-O-[ l-phenyl-5-methylmereapto-l ,2,4- triazolyl-( 3)l-thiophosphate A mixture consisting of 17.8 g of l-phenyl-S-methylmercapto-3-hydroxy-l,2,4-triazole, 16.2 g of0,0-diethylthiophosphoric acid chloride and 8.7 g of triethylamine in200 ml of acetone is refluxed for 6 hours. The precipitated salts areseparated, and the solvent evaporated off in vacuo. The residue is takenup in 250 ml of ethyl acetate, and washed with dilute hydrochloric acidand water. The solvent is evaporated off to thus obtain the compound ofthe formula in the form of pale yellow oil.

f. (),0-Diethyl-0-[ 5 -isopropyl-mercapto-l ,2,4-triazolyl- (3)]-thiophosphate A mixture consisting of l9.l g S-isopropylmercapto-3hydr oxy-l ,2,4-triazole, M.P. l39-l4lC, and l8.2 gof potassium carbonate in 250 ml of acetonitrile is refluxed for half anhour. An addition is then made dropwise within 10 minutes of 22.6

g of 0,0-diethyl-thiophosphoric acid chloride at a temperature of 5055C,and stirring subsequently carried out for 10 hours at 60-65C. Aftercooling to 20C, the precipitated salts are filtered off. The solvent isevapo rated off in vacuo, the crude product chromatographed throughsilica gel, and the compound of the formula CH3 C i n HS lrrrwc H) 3 N 25 2 obtained as pale yellow oil.

g. 0,0-Diethyl-0-[ l-phenyl-S-methylsulphinyl-l ,2,4- triazolyl-( 3)l-thiophosphate I80 g ofl-phcnyl-5-mothylsulphinyl-3-hydroxyll,2,4-triazole, M.P. 175C, and 11.1g of potassium carbonate in 500 ml of acctonitrile are refluxed for 2hours, and then cooled to 40C. An addition is made dropwise of 15.2 g of0,0-diethyl-thiophosphoric acid chloride, and the mixture again refluxedfor 2 hours. The undissolved salts are filtered off and the solvent thenevaporated off in vacuo to obtain the compound of the formula 18 in theform of pale yellow oil.

h. O-O-diethyl-0-[ l -phenyI-S-methylsulphonyl-l ,2,4- triazolyl-( 3)]-thiophosphate in the form of yellow oil.

The following compounds are obtained in an analogous manner;

@N N R -N-- N X 3 A l i 20 30 R oi z 011 -5 N O-P(OC H o 15551 2 N R R1R2 R R X Physical data on cH s c 3 0 c a s t l 1 CH3 cH so c r1 o 0235 sCH5 cH so c rr 0 C2H5 s CH5 crr s c11 0 ctr s CH3 cH s (n)c H s C285 sCH cn s c 11 c 11 s CH CHBS 0H 0 14 S CH3 CH3S CH3 (n) C H s CH3 011 s(n)C5H S c 11 5 CH3 cu s (n)C H S C2H5 0 CH3 CHBS Q c r1 s CH3 CH3S CHBS0 11 S CH 0 11 5 C2H50 C2H5 s CH3 c H s c14 0 on s CH3 c H s (n)C H S c11 3 Continued R1 R2 R3 R x Physical data c u s (n)C H S c n s Q c n so0 11 0 c 11 5 0 11 50 011 0 CH3 s Q (i)C H S c H 0 (2 1-1 8 11 2 51,5515 (l)c n s c11 0 cu s Q H s (n)C H S 0 11 S n 2o 1,5757 (1)c n s 011 0 x1 s p (n)C H S 0 11 0 0 H s n eoi 1,5478 Q (n)C H S c11 0 CH3 s(sec.)C H S; c11 0 CH3 s 1Q. 011 s c n o c u s C c11 5 cn o CH3 s C1 C16CH3S (n)C3H S C2H5 8 61C ca s C2H5 c n 8 (31C cn so c a o 0 11 S 61C} 32 2 5" 2 5 S GHQ c n s c u o 0 11 s 3% (111 s c u o c 11 5 CH3 C1 cn s 011 0 C2H5 s 011 5 0 11 0 c 11 5 9 CH S C1 3 (n)C H S c 11 5 cn pzi} cu sc n o 0 11 s 01 E 011 s (n)C H S C2H5 8 EXAMPLE 3 decemlineata) on thepotato plants. The test was carried A. Insecticidal Stomach PoisonAction Tobacco and potato plants were sprayed with a 0.05% aqueousactive substance emulsion (obtained from a l()% emulsifiableconcentrate).

After the drying of the coating, Egyption cotton leaf worms (SpudopleraIimrulis) were placed on the tobacco plants, and Colorada beetle larvae(Leplinomrsu out at 24C with 60 percent relative humidity.

The compounds according to Example 2 exhibited in the above test stomachpoison action against Spodoptera litoralis and Lcptinotarsadecemlineata.

8. Systemic lnsecticidal Action In order to determine the systemicaction. rooted bean plants (Vicia fuha) were placed into a 001 per-EXAMPLE 4 Action Against Chilo Suppressalis Rice plants of the typeCaloro were planted, 6 plants per pot, in plastic pots have a topdiameter of l7 cm, and grown to a height of ca. 60 cm. Infestation withChilo suppressalis larvae (L; 3-4 mm long) was carried out 2 days afterapplication of the active substance in granule form (amount applied 8 kgof active substance per hectare) to the paddy water. The evaluation ofthe insecticidal action was made 10 days after application of thegranules.

The compounds according to Example 2 were effective against Chilosuppressalis in the above test.

EXAMPLE Sterilised compost soil was homogeneously mixed with a wettablepowder containing 25 percent of active substance, so that an appliedamount of 8 kg of active substance per hectare resulted.

Young zucchetti plants (Cucumis papa) were potted with the treated soilin plastic pots (three plants per pot of 7 cm diameter). The said potswere infested immediately afterwards with 5 Aulacophora femoralislarvae, 5 Pachmoda larvae and 5 Chorlophila larvae, respectively. Theassessment of the results was made 4, 8, l6 and 32 days afterinfestation with the larvae.

In the case of 80-100 percent destruction on the first assessment, arepeated infestation was carried out, 5. larvae being placed into thesame sample of soil with 3 new zucchetti plants. Where the action wasless than 80 percent, the remaining larvae were left in the test soiluntil the next control assessment. If a substance with an applied amountof 8 kg per hectare effected a 100% destruction, then subsequent testswere made with 4 and 2 kg of active substance per hectare, respectively.

The compounds according to Example 2 were effective in the above testagainst Aulacophora femoralis larvae, Pachmoda larvae and Chlortophilalarvae.

EXAMPLE 6 Action Against Ticks A. Rhipit'ephalus Bursa In each case, 5adult ticks were placed into one small glass test tube and 50 ticklarvae into another; the test tubes were then immersed for l to 2minutes in 2 ml of an aqueous emulsion from a dilution series of I00,10, l and 0.1 ppm of test substance. The tubes were then sealed with astandardised cotton plug, and inverted so that the activesubstanceemulsion could be absorbed by the cotton wool.

An evaluation in the case of the adults was made after 2 weeks, and inthe case of the larvae after 2 days. There were two repeats for eachtest.

The compounds according to Example 2 were effective in the above testagainst adults and larvae of Rhipicephalus bursa.

v 36 B. Boophilus Microplus (Larvae) With a dilution series analogous tothat in Test A. tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (the resistance is with respect todiazinon compatibility).

The compounds according to Example 2 were effective in these testsagainst adults and larvae of Rhipicephalus bursa and against sensitiveand OP-resistant larve, respectively, of Boophilus microplus.

EXAMPLE 7 Acaricidal Action Phaseolus vulgaris (bush beans) wereinfested,"l2 hours before the test for acaracidal action, with aninfested piece of leaf from a mass culture of Tetranychus urticae. Thetransferred mobile stages were sprayed with the emulsified testpreparations from a chromatographysprayer in a manner ensuring norunning off of the spray liquor. An assessment was made after 2 to 7days, by examination under a binocular, of the living and of the deadlarvae, adults and eggs, and the results expressed in percentages. Thetreated plants were kept during the holding time in greenhousecompartments at 25C.

The compounds according to Example 2 were effective in the above testagainst adults, larvae and egges of Telranychus urticae.

EXAMPLE 8 Action Against Soil Nematode In order to test the actionagainst soil nematodes the active substances were added, in theconcentration stated in each case, to soil infested withrootgallnematodes (Meloidogyne arenaria), and the whole intimatelymixed. In the one test series, tomato seedlings were planted immediatelyafterwards in the thus prepared soil, and in the other test seriestomatoes were planted after a waiting time of 8 days.

For an assessment of the nematicidal action, the galls present on theroots were counted 28 days after the planting and sowing, respectively.

The active substances according to Example 2 exhibited in this test agood action against Meloidogyne arenaria.

We claim:

1. A compound for the formula wherein R represents hydrogen, C C alkyl,C -C cycloalkyl, phenyl, phenyl substituted by methoxy, halogen or C,Calkyl, benzyl or phenethyl,

R represents C C alkylthio, C -C, alkylsulphinyl C C alkylsulphonyl,phenthio, phenylsulphinyl, phenylsulphonyl, benzylthio, benzylsulphinylor benzylsulphonyl,

R represents C,C alkyl, C,-C, alkoxy, C -C alkylthio or phenyl,

R represents C C alkyl, and

X represents oxygen or sulphur.

2. A compound according to claim 1, wherein

1. A COMPOUND FOR THE FORMULA
 2. A compound according to claim 1,wherein R1 represents hydrogen, C1-C6-alkyl, cyclopentyl, cyclohexyl,benzyl, phenethyl, phenyl, 3-chlorophenyl, 3-methylphenyl,3-methyl-4-chlorophenyl, 2-methyl-4-chlorophenyl, 4-isopropylphenyl,3-chloro-4-methoxyphenyl or 3,4-dichlorophenyl, R2 representsC1-C5-alkylthio, C1-C5-alkylsulphinyl, C1-C5-alkylsulphonyl, phenthio,phenylsulphinyl, phenylsulphonyl or benzylthio, benzylsulphinyl,benzylsulphonyl, R3 represents methyl, ethyl, methoxy, ethoxy,C1-C5-alkylthio or phenyl, R4 represents methyl, ethyl or propyl, and Xrepresents oxygen or sulphur.
 3. The compound according to claim 2O,O-Diethyl-0-(1-isopropyl-5-methylmercapto-1,2,4-triazolyl(3))-thiophosphate.
 4. The compound according to claim 2O,O-Diethyl-0-(1-methyl-5-isopropylmercapto-1,2,4-triazolyl(3))-thiophosphate.
 5. The compound according to claim 2O,O-Diethyl-0-(1-methyl-5-methylmercapto-1,2,4-triazolyl(3))-thiophosphate.6. The compound according to claim 2O-Ethyl-S-propyl-0-(1-isopropyl-5-methylmercapto-1,2,4-triazolyl(3))-dithiophosphate.
 7. The compound according to claim 2O-Ethyl-S-propyl-0-(1-phenyl-5-methylmercapto-1,2,4-triazolyl(3))-dithiophosphate.
 8. The compound according to claim 2O-Ethyl-S-propyl-0-(1-methyl-5-isopropylmercapto-1,2,4-triazolyl(3))-dithiophosphate.